Metallurgical process.



L. F. VOGT.

METALLURGICAL PROCESS.

APPLIOATION FILED JULY 21, 1913,

1,129,029. Patented Feb.16,1915.

LOUIS F. VOGT, OF WASHINGTON, PENNSYLVANIA,- ASSIGNOR T0 STANDARD('JHIEJMIICALl COMPANY, OF PITTSBURGH, PENNSYLVANIA.

lltlIETALLU'RGICAL PROCESS.

Specication of Letters ltatent. Patented Feb. i6, 1915'.

Application filed July 21, 1913. Serial No. 780,339.

To all lwhom t may concern:

Be it known that I, Louis F. Voer, of

Washington, in the county of Washington and State of Pennsylvania, haveinvented certain new and useful Improvements in Metallurgical Processes;and I do hereby' '-to recover these constituents in maximum quantities.

A further object is to provide a process for the treatment ofradium-bearing ore,

. the treatment of ores as hereinafter set forth and pointed out in theclaims. 4 The accompanying drawing is a diagrammatical illustration ofmy improved process. The ore (such for example as carnotite ore) willpreferably be first concentrated in any approved manner or it may bemerely comminuted (step A). The pulverulent concentrate or ore will'then be roasted in the presence of sodium chlorid and steam (step B),the latter being employed for oxidizing purposes. The roasted ore lwillnext be leached with water to remove the greater part of the vanadiumcontent. To the water used in this step of the process, a small amountof sodium carbonate will be added to convert any possjrle radium orbarium chlorid to the carbonate form and prevent theexistence of radiumor barium in soluble form in the sodium vanadate lrquor (step C). Afterremoving the sodium vanadate liquor (which maybe stored for subsequenttreatment), the solid material or sludge, will be leached with mineralacid,

preferably sulfuric acid, to recover the uranium and suchvanadium asmay, remain lin the material, insolution. If an acid other than sulfuricbe used, sulicient sulfuric acid should be` added to form an insolubleradium sulfate and thus prevent any radium con` tent'ofthesludge fromgoing vinto suutioir.l

(step D). The sludge resulting from this step of the process willcomprise insoluble radium and barium salts and.l the4- liquor willconsist of uanyl and vanadyl salts and impurities, in solution.

After separation' of the liquor from the sludge, said liquor will beneutralized with suiicient sodium carbonate to precipitate im# puritiessuch as iron, alumina, silica, etc., together with a large portion ofthe uranium and vanadium. If'the solution contains impurities insufliciently large quantity, all of the uranium and vanadium contentwould be precipitated.

To the mixture (the solution and'precipitate) resulting from theneutralizing step above described, an excess of sodium carbonate will beadded, and the mixture will be boiled, the purpose of this step being toleach out the uranium and vanadium contained in the precipitate, leavingthe impurities in the precipitate (step A D1). The uranium and vanadiumwill now be in solution as sodium compounds of these elements. Thissolution or liquor-will then be separated from the precipitate byfiltering or otherwise, and will be treated to recover the uranium andvanadium, as follows: The. solution of lsodium compounds of uranium 4andvanadium is treated in a suitable tank with a salt of lead,-such, forexample as lead sulfate or carbonate, the whole being agitated andboiled with steam (step D2). The lead salt will react with the vanadiumcontained in the liquor and form insoluble lead vanadate, while theuranium will remain in solution. The lead vanadate will then beseparated from the precipitate or sludge by filtration, decantation orotherwise, and the uranium solution (sodium uranyl carbonate) which isnow free from vanadium will be treated for the recovery of the uranium,as follows: The sodium uranyl carbonate solution will be boiled withsteam or otherwise and sufficient sodiu and free alkali.

um hydrate will be added to completely precipitate the uranium as sodiumuranate (step D3). This precipitate will be separated from the solutionand then Washed and dried, ready for commercial use.

The lead vanadate resulting from the lead treatment 'above described maybe boiled i n sulfuric acid to .leach out the vanadium leaving the leadin the form of lead sulfate which may be used again for removingvanadium from the uraniumvanadium solutions hereinbefore described.

The solid matter or sludge, referred to as resulting from step D, andcomprising insoluble radium and barium salts and impurities, will beWashed, filtered and dried. The dry material will ythen be thoroughlymixed with sufficient sodium carbonate to flux the mixture whenheated ina furnace. The mixture is then subjected to sufficient heat(approximately 2200 F.) ina suitable furnace, to fuse the mixture andrender the same Huid, (step lE).A During this fusing` step, thefollowing reactions have takenplace: Silica has largely become sodiumsilicate, and the radium, barium, lime, iron, etc., have become theirrespective carbonates. The iiuid material, upon being discharged fromthe furnace, will be spread out in a suitable manner to permit it tocool in the form of thin Hakes (step E).

The cooled and flaked matte, consisting of carbonates of radium, barium,iron, lime, etc., together with sodium silicate and excess of sodiumcarbonate, will be treated with water and agitated in a suitablecontainer, so that the sodium silicate contained in the material will bedissolved, leaving the insoluble carbonates suspended in the liquor(step F). These insoluble carbonates will then be separated from theliquor containing sodium silicate, by filtration or otherwise, so thatthe carbonates may be recovered freed from a large portion of the silicawhich the material contained. The carbonates will then be washed withwater to remove' any remaining sodium silicate The said carbonates willthen be comminuted in any suitable manner and mixed in water, thusmaking an aqueous mixture in which the comminuted carbonates are held insuspension. The aqueous mixture of carbonates is introduced into asuitable tank containing mineral acid, preferably hydrochloric, inquantity suiiicient to dissolve the carbonates completely, leaving aslight excess of free acid (step G). By now adding sulfuric acid to thissolution, radium and barium sulfates are precipitated and remaininsoluble, (step G1), while the impurities (such as iron, aluminum andlime) remain in solution. The

sulfates ofradium and barium will then be separated in any suitablemanner from the refuse liquor containing the impurities, and then dried.The dried sulfates of radium and barium, which are now of relativelyhigh radium and barium content, will now be thoroughly mixed withcomminuted coke or other suitable carbonaceous material and a suitablechlorid (for example, calcium chlorid), and roasted (step H). During theroasting, the sulfates of radium and barium are converted 4to chlorids.The roasted mixture will then be leached with .water to dissolve thechlorids (step I), leavfrom the barium is accomplished by systematicfractional crystallization.

Having fully described my invention what I claim as new and desire tosecure by Letters-Patent, is

1. The herein described method of reducing carnotite ore for therecovery of the radium content, consisting in roasting the ore in thepresence of sodium chlorid and subsequently subjecting the material tosuccessive treatments to remove the vanadium and then the uraniumcompounds, leaving the radium and barium as insoluble compounds,4 thenconverting said radium and barium compounds to av soluble state insolution, and finally subjecting the solution of barium and radiumcompounds to systematic fractional crystallization and recovering radiumsalt free from other compounds as a final product.

2. The herein described process of treating ore containing vanadium,uranium and radium, for the successive .elimination of vanadium anduranium and the final recovery of a salt of radium, consisting inroasting the ore in the presence of sodium chlorid and an oxidizingagent, leaching the roasted.- Amaterial and 'obtaining a solution ofsodium vanadate, separating the solution from the sludge, leaching saidsludge with a solution of sulfuric acid-and obtaining uranyl andvanadyl'lsalts in solution, separating the solution from this sludge,then subjecting the last-mentioned sludge to treatment for theelimination of the constituent materials from the radium content,treating said radium content to a chlorid, leaching the roasted mixtureand' recovering radium chlorid in solution.

5. The herein described process consisting in fusing material containingradium and barium, with an alkali carbonate; then leaching with Water;then dissolving the resultant radium and barium carbonates in acid; thenadding sulfuric acid; recovering radium and barium sulfates; roastingsaid sulfates with -carbonaceous materia] and a chlorid; leaching theroasted mixture and recovering chlorids of radium and barium insolution; and then subjecting said solution of adium and barium chloridsto systematic fractional crystallization to remove the barium andkrecover radium chlorid.

6. The herein described process consisting in roasting ore containingradium, uranium and vanadium inthe presence of sodium chlorid and anoxidizing agent; leaching the roasted material and obtaining a solutionof sodium vanadate free from ra.- dium; leaching the resultant sludgewith fluid containing sulfuric acid and obtaining a solution of uraniumand vanadium and free from radium; then treatmg the resultant sludge forrecovery of radium.

In testimony whereof, I have signed this specliicatlon 1n the presenceof two subscribing witnesses.

LOUIS 1". V(.)G'l`. Witnesses: y

R. S. FERGUSON, S. C. HILL.

